CA1164465A - Preparation of phenoxy-azolyl-butanone derivatives - Google Patents
Preparation of phenoxy-azolyl-butanone derivativesInfo
- Publication number
- CA1164465A CA1164465A CA000385990A CA385990A CA1164465A CA 1164465 A CA1164465 A CA 1164465A CA 000385990 A CA000385990 A CA 000385990A CA 385990 A CA385990 A CA 385990A CA 1164465 A CA1164465 A CA 1164465A
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- Canada
- Prior art keywords
- process according
- water
- temperature
- acid
- formula
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
ABSTRACT
In the preparation of a phenoxy-azolyl-butanone derivative of the formula in which X is a halogen atom, Y is a hydrogen or halogen atom, and Az is an imidazolyl radical or a 1,2,4-triazolyl radical, wherein dichloropinacolin of the formula C12CH-CO-C(CH3)3 is reacted with an azole of the formula Az-H
and a phenol of the formula
In the preparation of a phenoxy-azolyl-butanone derivative of the formula in which X is a halogen atom, Y is a hydrogen or halogen atom, and Az is an imidazolyl radical or a 1,2,4-triazolyl radical, wherein dichloropinacolin of the formula C12CH-CO-C(CH3)3 is reacted with an azole of the formula Az-H
and a phenol of the formula
Description
The present invention relates to an unobvious process, which can be used industrially, for the preparation and purification of oe rtain known phenoxy-azolyl-butanone derivatives.
It has already been disclosed that phenoxy-azolyl-butanone derivatives can be obtained when dihalogenopinacolins are reacted with 1,2,4-triazole and phenols in the presen oe of an acid-binding agent (such as potassium carbonate) and in the presen oe of a polar solvent (such as a oe tone) at temperatures between O and 150 & (see our ~E-AS (German Published Specification) 2,406,665).
Hcwever, this process has the disadvantage that, especially in the case of the preparation on an industrial scale, competing reactions lead to the in-creased formation of by-products which considerably reduce the content of the de-sired end product. In addition, the spaoe /time yield is unsatisfactory because of a troublesome and time-consuming working up pro oe dure.
The present invention now provides a pro oe ss for the preparation of a phenoxy-azolyl-butanone derivative of the general formula X- ~ -O~CH-CO-C(CH3)3 (I) Az in which X represents a halogen atom, Y represents a hydrogen or halogen atom and Az represents an imidazolyl radical or 1,2,4-triazolyl radical, in which dichloropinacolin of the formula Cl CH-CO-C(CH ) (II) is reacted with an azole of the general formLla ~., .- ~
Az-~ (III) in which Az has the meaning given above, and a phenol of the general formula x4~c~
y in which X and Y have the meaning given above, in the presence of an acid-binding agent, ch æ acterised in that the reaction is carried out in the presen oe of a water-immiscible organic solvent at a tempera-ture between 40 and 150C, the crude end product of the formLla (I) is left in solution, without changing the solvent, and, for purification of the product, in the same solution, a mineral acid is added at a temperature between 0 and +80C, the salt is separated off and the pure end product of the formula (I) is isolated from the salt. The pro oe ss of the present invention gives the phenoxy-azolyl-butanone derivatives of formula (I) in gcod yield and purity, even on an indust-rial scale.
It is to be described as exoe ptionally surprising that the phenoxy-azolyl-butanone deri~atives of the formwla (I), which after all are kncwn to be-long to the group of O,N-a oe tals, are stable in the prese~ce of mineral acid under the precipitation conditions (at 0 to 80 C), as it is generally known that O,N-a oe tals can easily be split by acid catalysis. This is all the more surpris-ing sin oe the salt of the compound of the formLla (I) d oe s not precipitate in-stantaneously, but is exposed to attack by excess mineral acid for scme time.
~.
~ 16~65 It is also surprising that the water-immiscible ketones (such as methyl isobutyl ketone), preferably to be used as organic solvents for the procedure according to the invention, can ~e employed for the salt precipitation. In part-icular, it is generally known that, for example, acetone, as a solvent which is structurally ccmparable to methyl isobutyl ketone, very readily undergoe s con-densation reactions under the catalytic influence of mineral acids, such as, in particular, of the sulphuric acid which is preferably to be used according to the invention. m e stability of methyl isobutyl ketone in the presence of concen-trated sulphuric acid in the temperature range of 0 to 80C to be used was thus hardly to be expected.
m e procedure, according to the invention, by which the process is carried out has the advantage that the desired product is obtained with a content of >97~, even in the case of preparation on an industrial scale, and at the same time the space/time yield is good.
In the general formNla I, X preferably represents a chlorine atom, Y
preferably represents a hydrogen or chlorine atom and Az preferably represents the l,2,4-triazol-l-yl radical.
The pro oe ss can preferably be carried out by the followlng pro oe dure:
1 to 1.5 I~moles of dichloropinacolin and l to 4 Kmoles of acid-b m ding agent in a water-immiscible ketone (such as methyl isobutyl ketone) or an arcmatic hydro-carbon (such as toluene) are reacted with a mixture of l to 1.5 Kmoles of azole (1,2,4-triazole or imidazole) and l Km~le of a phenol (such as 4-chlorophenol) at 40 to 120C. This method of addition is preferred; however, it is also possible to initially introduce the phenol, the azole and the a d d-binding agent and to add dichloropinacolin. The reaction time is 8 to 15 hours. For w~rking up, water is added to the reaction mixture and the phases are then separated. The organic phase, which contains the desired reaction prcduct, is washed with dilute 1 ~644~
sodi~n hydroxide solution for further rem~oval of undesired by-products. After renewed phase separation, mineral acid (such as sulphurie acid) is added to the organic phase at 0 to 80&.
The salt is separated off and the free base of the for~rmla (I) is o~
tained therefrorn in the cust~nary manner with a content of >97g6 (determined by gas chrcmatography).
Possible water-immiscible organic solvents are, in particular: rnethyl isobutyl ketone or other water-immiscible ketones.
It is furthern~re also possible to use other water-immiscible solvents, 10 such as arornatic hydrocarbons. Examples which may be m~entioned are: toluene, xylene and chlorobenzene.
Possible acid-binding agents for the reaction are any of the custanary organic and, in particular, inorganic acid-binding agents. Examples which may be nlentioned are: tertiary amines (such as triethylamine or dilrethylcyclohexylamine), alkali metal hydroxides ~sueh as sodiurn hydroxide or potassium hydroxide), alkali metal carbonates (such as sodiurn carbonate or potassiurn carbonate), and alkaline earth rnetal hydroxides or carbonates (sueh as caleiurn hydroxide or ealeiurn earbon-ate) .
Sulphurie acid, for example eoncentrated sulphurie aeid, is preferably 20 used as the mineral aeid required for separating out the salt in the process aecording to the invention.
The reaetion is earried out at a temperature between 40 and 150C, pre-ferably at a temperature between 40 and 120&.
me purification step aecording to the invention is earried out at a temperature between 0 and 80C, preferably at a temperature between 20 and 70C.
In carrying out the reaction~ 1 to 1.5 Kmoles of dichloropinaeolin, 1 to 1.5 Rrnoles of the azole and 1 to 4 Rmoles of aeid-binding agent are preferably employed per ~le of phenol.
1 164~65 The ccmpo~nds of the formula (I) have a very good fungicidal activity (see our LE-AS (German Published Specification) 2,201,063~. They can be used, for example, with particularly yood success as agents against pawdery mildew ~asleaf fungicides) and against cereal diseases, such as cereal rust (as a seed dressing).
The process according to the invention (with a ocmparison with the state of the art) is illustrated with the aid of the following Preparative Example:
Preparative Exa~ple on an industrial scale Cl- ~ -O-CH-C0-C(CH3)3 ~ N~N
N ~
a) pro oe ss according to the invention 197 kg (1,165 les) of dichloropinaoolin and 420 kg (3,040 moles) of potassium carbonate in 640 kg of methyl isobutyl ketone were warmed to 90 & in a3,000 litre stirred kettle. A mixture of 129 kg (1,000 moles) of 4-chlorophenol and 76.4 kg (l,lO0 mDles) of l,2,4-triazole was added to the kettle. The mixturewas subsequently stirred at 90 to 95C for 10 hours and cooled to 50 & and l,400 kg of water were added. The mixture was subsequently stirred for 30 minutes and the aqueous phase was then separated off. The organic phase was washed with 350 kg of dill~te sodium hydroxide solution and then with 50 kg of water.
76 kg of 96~ strength sulphuric acid were allcwed to run in at 40 & and the mixture was then cooled to 10C. The precipitate which had separated out waswashed with 300 kg of methyl isobutyl ketone and hydrolysed in a mixture of 400 kg of methyl isobutyl ketone, 400 kg of water and lO0 kg of 45% strength sodium ^~'.
6 ~
hydroxide solution. The aqueous phase was separated off and the organic phase was con oe ntrated. 183 kg (61% of theory, relative to the 4-chlorophenol employed) of l-(4-chlorophenoxy)-3,3-d~methyl-1-(1,2,4-triazol-1-yl)-butan-2-one with a melting point of 75 to 76C and a content of 97.5% (determined by gas chromatography) were obtained.
b) known pro oe ss (batch on an industrial scale in accordan oe with the instruc-tions of ~E-AS (German Published Specification) 2,406,665).
550 kg of acetone were initially introdu oe d into a 3,000 litre stirred kettle. 104 kg (1,500 moles) of 1,2,4-triazole, 634 kg (4,600 mDles) of potas-sium carbonate and 193 kg (1,500 moles) of 4-chlorophenol were added, whilst stirring. The mixture was heated to the reflux temperature, and 330 kg (1,950 moles) of dichloropinacolin, dissolved in 240 kg of aoe tone, were added. ~hen the addition had ended, the mixture was stirred under reflux for 16 hours. It was allowed to cool to roan temperature and was filtered. The filtrate was con-oe ntrated by distilling off the solvent. The residue was taken up in 1,300 kg of toluene and the mixture was washed first with a mixture of 250 kg of water and 134 kg of con oe ntrated hydrochloric acid and then again with 400 kg of water.
After conoentrating the mixture, 408 kg (61% of theory, relative to the 4-chloro-phenol employed) of l-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-
It has already been disclosed that phenoxy-azolyl-butanone derivatives can be obtained when dihalogenopinacolins are reacted with 1,2,4-triazole and phenols in the presen oe of an acid-binding agent (such as potassium carbonate) and in the presen oe of a polar solvent (such as a oe tone) at temperatures between O and 150 & (see our ~E-AS (German Published Specification) 2,406,665).
Hcwever, this process has the disadvantage that, especially in the case of the preparation on an industrial scale, competing reactions lead to the in-creased formation of by-products which considerably reduce the content of the de-sired end product. In addition, the spaoe /time yield is unsatisfactory because of a troublesome and time-consuming working up pro oe dure.
The present invention now provides a pro oe ss for the preparation of a phenoxy-azolyl-butanone derivative of the general formula X- ~ -O~CH-CO-C(CH3)3 (I) Az in which X represents a halogen atom, Y represents a hydrogen or halogen atom and Az represents an imidazolyl radical or 1,2,4-triazolyl radical, in which dichloropinacolin of the formula Cl CH-CO-C(CH ) (II) is reacted with an azole of the general formLla ~., .- ~
Az-~ (III) in which Az has the meaning given above, and a phenol of the general formula x4~c~
y in which X and Y have the meaning given above, in the presence of an acid-binding agent, ch æ acterised in that the reaction is carried out in the presen oe of a water-immiscible organic solvent at a tempera-ture between 40 and 150C, the crude end product of the formLla (I) is left in solution, without changing the solvent, and, for purification of the product, in the same solution, a mineral acid is added at a temperature between 0 and +80C, the salt is separated off and the pure end product of the formula (I) is isolated from the salt. The pro oe ss of the present invention gives the phenoxy-azolyl-butanone derivatives of formula (I) in gcod yield and purity, even on an indust-rial scale.
It is to be described as exoe ptionally surprising that the phenoxy-azolyl-butanone deri~atives of the formwla (I), which after all are kncwn to be-long to the group of O,N-a oe tals, are stable in the prese~ce of mineral acid under the precipitation conditions (at 0 to 80 C), as it is generally known that O,N-a oe tals can easily be split by acid catalysis. This is all the more surpris-ing sin oe the salt of the compound of the formLla (I) d oe s not precipitate in-stantaneously, but is exposed to attack by excess mineral acid for scme time.
~.
~ 16~65 It is also surprising that the water-immiscible ketones (such as methyl isobutyl ketone), preferably to be used as organic solvents for the procedure according to the invention, can ~e employed for the salt precipitation. In part-icular, it is generally known that, for example, acetone, as a solvent which is structurally ccmparable to methyl isobutyl ketone, very readily undergoe s con-densation reactions under the catalytic influence of mineral acids, such as, in particular, of the sulphuric acid which is preferably to be used according to the invention. m e stability of methyl isobutyl ketone in the presence of concen-trated sulphuric acid in the temperature range of 0 to 80C to be used was thus hardly to be expected.
m e procedure, according to the invention, by which the process is carried out has the advantage that the desired product is obtained with a content of >97~, even in the case of preparation on an industrial scale, and at the same time the space/time yield is good.
In the general formNla I, X preferably represents a chlorine atom, Y
preferably represents a hydrogen or chlorine atom and Az preferably represents the l,2,4-triazol-l-yl radical.
The pro oe ss can preferably be carried out by the followlng pro oe dure:
1 to 1.5 I~moles of dichloropinacolin and l to 4 Kmoles of acid-b m ding agent in a water-immiscible ketone (such as methyl isobutyl ketone) or an arcmatic hydro-carbon (such as toluene) are reacted with a mixture of l to 1.5 Kmoles of azole (1,2,4-triazole or imidazole) and l Km~le of a phenol (such as 4-chlorophenol) at 40 to 120C. This method of addition is preferred; however, it is also possible to initially introduce the phenol, the azole and the a d d-binding agent and to add dichloropinacolin. The reaction time is 8 to 15 hours. For w~rking up, water is added to the reaction mixture and the phases are then separated. The organic phase, which contains the desired reaction prcduct, is washed with dilute 1 ~644~
sodi~n hydroxide solution for further rem~oval of undesired by-products. After renewed phase separation, mineral acid (such as sulphurie acid) is added to the organic phase at 0 to 80&.
The salt is separated off and the free base of the for~rmla (I) is o~
tained therefrorn in the cust~nary manner with a content of >97g6 (determined by gas chrcmatography).
Possible water-immiscible organic solvents are, in particular: rnethyl isobutyl ketone or other water-immiscible ketones.
It is furthern~re also possible to use other water-immiscible solvents, 10 such as arornatic hydrocarbons. Examples which may be m~entioned are: toluene, xylene and chlorobenzene.
Possible acid-binding agents for the reaction are any of the custanary organic and, in particular, inorganic acid-binding agents. Examples which may be nlentioned are: tertiary amines (such as triethylamine or dilrethylcyclohexylamine), alkali metal hydroxides ~sueh as sodiurn hydroxide or potassium hydroxide), alkali metal carbonates (such as sodiurn carbonate or potassiurn carbonate), and alkaline earth rnetal hydroxides or carbonates (sueh as caleiurn hydroxide or ealeiurn earbon-ate) .
Sulphurie acid, for example eoncentrated sulphurie aeid, is preferably 20 used as the mineral aeid required for separating out the salt in the process aecording to the invention.
The reaetion is earried out at a temperature between 40 and 150C, pre-ferably at a temperature between 40 and 120&.
me purification step aecording to the invention is earried out at a temperature between 0 and 80C, preferably at a temperature between 20 and 70C.
In carrying out the reaction~ 1 to 1.5 Kmoles of dichloropinaeolin, 1 to 1.5 Rrnoles of the azole and 1 to 4 Rmoles of aeid-binding agent are preferably employed per ~le of phenol.
1 164~65 The ccmpo~nds of the formula (I) have a very good fungicidal activity (see our LE-AS (German Published Specification) 2,201,063~. They can be used, for example, with particularly yood success as agents against pawdery mildew ~asleaf fungicides) and against cereal diseases, such as cereal rust (as a seed dressing).
The process according to the invention (with a ocmparison with the state of the art) is illustrated with the aid of the following Preparative Example:
Preparative Exa~ple on an industrial scale Cl- ~ -O-CH-C0-C(CH3)3 ~ N~N
N ~
a) pro oe ss according to the invention 197 kg (1,165 les) of dichloropinaoolin and 420 kg (3,040 moles) of potassium carbonate in 640 kg of methyl isobutyl ketone were warmed to 90 & in a3,000 litre stirred kettle. A mixture of 129 kg (1,000 moles) of 4-chlorophenol and 76.4 kg (l,lO0 mDles) of l,2,4-triazole was added to the kettle. The mixturewas subsequently stirred at 90 to 95C for 10 hours and cooled to 50 & and l,400 kg of water were added. The mixture was subsequently stirred for 30 minutes and the aqueous phase was then separated off. The organic phase was washed with 350 kg of dill~te sodium hydroxide solution and then with 50 kg of water.
76 kg of 96~ strength sulphuric acid were allcwed to run in at 40 & and the mixture was then cooled to 10C. The precipitate which had separated out waswashed with 300 kg of methyl isobutyl ketone and hydrolysed in a mixture of 400 kg of methyl isobutyl ketone, 400 kg of water and lO0 kg of 45% strength sodium ^~'.
6 ~
hydroxide solution. The aqueous phase was separated off and the organic phase was con oe ntrated. 183 kg (61% of theory, relative to the 4-chlorophenol employed) of l-(4-chlorophenoxy)-3,3-d~methyl-1-(1,2,4-triazol-1-yl)-butan-2-one with a melting point of 75 to 76C and a content of 97.5% (determined by gas chromatography) were obtained.
b) known pro oe ss (batch on an industrial scale in accordan oe with the instruc-tions of ~E-AS (German Published Specification) 2,406,665).
550 kg of acetone were initially introdu oe d into a 3,000 litre stirred kettle. 104 kg (1,500 moles) of 1,2,4-triazole, 634 kg (4,600 mDles) of potas-sium carbonate and 193 kg (1,500 moles) of 4-chlorophenol were added, whilst stirring. The mixture was heated to the reflux temperature, and 330 kg (1,950 moles) of dichloropinacolin, dissolved in 240 kg of aoe tone, were added. ~hen the addition had ended, the mixture was stirred under reflux for 16 hours. It was allowed to cool to roan temperature and was filtered. The filtrate was con-oe ntrated by distilling off the solvent. The residue was taken up in 1,300 kg of toluene and the mixture was washed first with a mixture of 250 kg of water and 134 kg of con oe ntrated hydrochloric acid and then again with 400 kg of water.
After conoentrating the mixture, 408 kg (61% of theory, relative to the 4-chloro-phenol employed) of l-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-
2-one were obtained as a viscous oil with a content of 66~ (determined by gas chromatography).
. .
. .
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a phenoxy-azolyl-butanone derivative of the general formula (I) in which X represents a halogen atom, Y represents a hydrogen or halogen atom and Az represents an imidazolyl radical or 1,2,4-triazolyl radical, in which dichloropinacolin of the formula C12CH - CO - C(CH3)3 (II) is reacted with an azole of the general forrnula Az - H (III) in which Az has the meaning given above, and a phenol of the formula in which X and Y have the meaning given above, in the presence of an acid-binding agent, characterised in that the reaction is carried out in the presence of a water-immiscible organic solvent at a temperature between 40 and 150°C, a mineral acid is added to the solution of the reaction product at a temperature between 0 and +80°C, the mineral acid salt of the phenoxy-azolyl-butanone so formed is separated off and the pure end product of the formula (I) is isolated from the salt.
2. A process according to claim 1, characterised in that the water-immiscible organic solvent used is a water-immiscible ketone.
3. A process according to claim 2, characterised in that the water-immiscible organic solvent used is methyl isobutyl ketone.
4. A process according to any of claims 1 to 3, characterised in that the mineral acid used is sulphuric acid.
5. A process according to any of claims 1 to 3, characterised in that in the starting materials X represents a chlorine atom, Y represents a hydrogen or chlorine atom and Az represents a 1,2,4-triazol-1-yl radical.
6. A process according to any of claims 1 to 3, characterised in that the reaction of the dichloropinacolin with the azole and the phenol is effected at a temperature between 40 and 120°C.
7. A process according to any of claims 1 to 3, characterised in that the mineral acid is added at a temperature between 20 and 70°C.
8, A process according to claim 1, characterised in that 1 to 1.5 Kmoles of dichloropinacolin, 1 to 1.5 Kmoles of the azo]e and 1 to 4 Kmoles of acid-binding agent are employed per Kmole of phenol.
9. A process according to claim 8, characterised in that the water-immiscible organic solvent used is a water-immiscible ketone.
10. A process according to claim 9, characterised in that the water-immiscible organic solvent used is methyl isobutyl ketone.
11. A process according to claim 10, characterised in that in the starting materials X represents a chlorine atom, Y represents a hydrogen or chlorine atom and Az represents a 1,2,4-triazol l-yl radical.
12, A process according to claim 11, wherein the mineral acid used is sulphuric acid and is added at a temperature between 20 and 70°C
13. A process according to claim 12, characterised in that the reaction of the dichloropinacolin with the azole and the phenol is effected at a temperature between 40 and 120°C.
14. A process according to claim 13, characterised in that 1 to 1.5 Kmoles of dichloropinacolin, 1 to 1.5 Kmoles of the azole and 1 to 4 Kmoles of acid-binding agent are employed per Kmole of phenol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803035022 DE3035022A1 (en) | 1980-09-17 | 1980-09-17 | METHOD FOR PRODUCING AND PURIFYING PHENOXYAZOLYL BUTANONE DERIVATIVES |
| DEP3035022.2 | 1980-09-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1164465A true CA1164465A (en) | 1984-03-27 |
Family
ID=6112162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000385990A Expired CA1164465A (en) | 1980-09-17 | 1981-09-16 | Preparation of phenoxy-azolyl-butanone derivatives |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4388465A (en) |
| EP (1) | EP0047941B1 (en) |
| JP (1) | JPS5781474A (en) |
| BR (1) | BR8105922A (en) |
| CA (1) | CA1164465A (en) |
| DE (2) | DE3035022A1 (en) |
| DK (1) | DK150198C (en) |
| HU (1) | HU185957B (en) |
| IL (1) | IL63823A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MXPA01006553A (en) * | 1999-12-14 | 2002-03-14 | Avon Prod Inc | A skin care composition that mediates cell-to-cell communication. |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2406665C3 (en) * | 1974-02-12 | 1978-11-16 | Bayer Ag, 5090 Leverkusen | Process for the preparation of 1,2,4-triazole derivatives |
| DE2713777C3 (en) * | 1977-03-29 | 1979-10-31 | Bayer Ag, 5090 Leverkusen | Process for the preparation of l-azolyl-33-dimethyl-l-phenoxy-butan-2-ones |
| DE2743767A1 (en) * | 1977-09-29 | 1979-04-12 | Bayer Ag | DIASTEREOMERS TRIAZOLYL-0, N-ACETALS, METHOD FOR THEIR MANUFACTURING AND THEIR USE AS FUNGICIDES |
| DE2850057A1 (en) * | 1978-11-18 | 1980-05-29 | Bayer Ag | DIASTEREOMER 1- (4-CHLORPHENOXY) - 1- (1-IMIDAZOLYL) -3,3-DIMETHYL-2-BUTANOL, METHOD FOR THE PRODUCTION AND USE THEREOF AS A MEDICINAL PRODUCT |
-
1980
- 1980-09-17 DE DE19803035022 patent/DE3035022A1/en not_active Withdrawn
-
1981
- 1981-09-05 EP EP81106979A patent/EP0047941B1/en not_active Expired
- 1981-09-05 DE DE8181106979T patent/DE3161598D1/en not_active Expired
- 1981-09-08 US US06/300,071 patent/US4388465A/en not_active Expired - Lifetime
- 1981-09-14 JP JP56144054A patent/JPS5781474A/en active Granted
- 1981-09-14 IL IL63823A patent/IL63823A/en not_active IP Right Cessation
- 1981-09-16 DK DK412781A patent/DK150198C/en not_active IP Right Cessation
- 1981-09-16 BR BR8105922A patent/BR8105922A/en unknown
- 1981-09-16 CA CA000385990A patent/CA1164465A/en not_active Expired
- 1981-09-17 HU HU812683A patent/HU185957B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IL63823A0 (en) | 1981-12-31 |
| HU185957B (en) | 1985-04-28 |
| JPS5781474A (en) | 1982-05-21 |
| BR8105922A (en) | 1982-06-08 |
| EP0047941A1 (en) | 1982-03-24 |
| JPH0224822B2 (en) | 1990-05-30 |
| EP0047941B1 (en) | 1983-12-07 |
| DK150198B (en) | 1987-01-05 |
| US4388465A (en) | 1983-06-14 |
| DK412781A (en) | 1982-03-18 |
| DE3161598D1 (en) | 1984-01-12 |
| DE3035022A1 (en) | 1982-04-22 |
| DK150198C (en) | 1987-07-06 |
| IL63823A (en) | 1985-06-30 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |